JP5801318B2 - Cosmetic treatment method comprising a compound that can be condensed in situ and an agent that blocks UV radiation - Google Patents

Description

  The present invention relates to a method for cosmetic treatment of the skin comprising a compound or group of compounds that can be condensed in situ and an agent that blocks UV radiation.

  Light irradiation with a wavelength of 280-400 nm allows the human epidermis to brown, and light with a wavelength of 280-320 nm, known as UV-B rays, can be harmful to the occurrence of sunburn. Involved in some red skin spots. Light having a wavelength of 320-400 nm, known as UV-A radiation, can lead to adverse skin changes, particularly with reduced elasticity and the appearance of wrinkles, leading to premature aging.

  Therefore, UV radiation must be blocked and there currently exists a protective cosmetic composition for human epidermis that contains an organic UV blocker that is active for blocking UV-A and UV-B radiation. .

  It is known that relatively large amounts of UV blockers must be used to achieve blocking levels against significant levels of UV-A and UV-B irradiation. However, these UV blockers show the following disadvantages when formulated at high contents: formulation instability and sensory defects. Furthermore, the photoprotective cosmetic compositions have their shielding effectiveness reduced under the conditions of use of sunscreen products, especially due to their low water resistance.

US5624663 EP669323 US2463264 US5237071 US5166355 GB2303549 DE19726184 EP893119 EP0832642 EP1027883 EP1300137 DE10162844 WO93 / 04665 DE19855649 EP0967200 DE19746654 DE19755649 EP-A-1008586 EP1133980 EP133981 WO04 / 006878 WO05 / 058269 WO06 / 032741 US6225467 WO2004 / 085412 WO06 / 035000 WO06 / 034982 WO06 / 034991 WO06 / 035007 WO2006 / 034992 WO2006 / 034985 EP-A-0518773 WO-A-92 / 06778 FR2315991 FR2416008 US4077441 US4850517 EP1562562 EP1151742 FR2869796 US5538793 EP-A-1579849 FR2466492 WO97 / 35842 EP903342 WO97 / 25970 FR2840806 FR2651126 EP-B-0425324

"Symmetrical Triazine Derivatives" IP.COM Journal, IP.COM INC West Henrietta, NY, US (September 20, 2004) Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965)

  Therefore, obtain an available photoprotective cosmetic composition that has a good level of blocking effectiveness obtained using a limited content of UV blocker and that shows a good level of water persistence It is considered necessary to do.

  Surprisingly, Applicant's company has a good level of blocking effectiveness obtained using a limited content of UV blocker and shows a good level of persistence against water It was shown that it is possible to obtain a usable photoprotective cosmetic composition. This is because Applicant's company has discovered that it is possible to form condensates in the surface of the skin or on the skin that impart properties that capture the UV blocking agent on the skin. This “trapping” layer is formed by the in situ condensation of at least one compound or group of compounds A described below.

The advantageous properties obtained by the process according to the invention are in particular:
-Properties that promote the uniform distribution of UV blockers on the surface of the skin,
-A property that provides a sufficient point of attachment for these UV blockers and stays in place when immersed in water and especially in water soluble or water dispersible blockers.

  In addition to the effect of enhancing the resistance of UV blockers on the skin, Applicant's company has discovered that the present invention can provide other benefits such as enhanced blocking effectiveness.

This principle is used as follows:
1—Application to the skin of a composition comprising an effective amount of monomer A capable of reacting with itself. Monomer A therefore has a reactive functional group that allows the reaction with itself to take place. These functional groups are referred to as “inter-monomer reactive functional groups”. Monomer A is selected such that it also has a reactive functional group referred to as a “capture functional group” after the reaction.

  2-Reaction of this monomer A with itself (or with another monomer B) on the skin, for example by condensation, especially when exposed to increased concentrations obtained by evaporation of the solvent medium containing it. This reaction results in the formation of a deposited layer on or in the skin. This deposited layer is not necessarily continuous, but may consist of a number of small linked domains.

  3- Application of a blocking agent to the condensate of monomer A obtained on the skin. The blocking agent can in particular react via a capture functional group, but can also react with one or more unreacted reactive groups, referred to as “inter-monomer reactive functional groups”.

  4-Chemical reactions occur with the formation of covalent or physical (ionic or hydrogen) bonds between the blocking agent and one or more capture functional groups. This has the effect of modifying the condensate on the skin. This reaction in particular makes the condensate insoluble while maintaining the blocking effectiveness of the applied UV-blocking agent (s), or even further strengthening it, thereby maintaining its persistence on the skin (water, Resistance to sweat, sebum, etc.) can be further increased.

The subject of the present invention is therefore a method for cosmetic treatment of the skin comprising
a compound or group of compounds _A capable of exhibiting at least one reactive functional group FA that is condensed in situ and free after condensation, and
- covalent or physical by reaction with functional groups F _A (ionic, hydrogen) containing a reactive functional group F _C capable of forming a bond, blocking agent C which blocks UV radiation
A method comprising the application to the skin.

  This is because the applicant's company was able to demonstrate that the application of these two compounds to the skin can provide local and rapid long-lasting blocking properties. It is.

  The acquisition layer is formed in situ in the surface layer of the skin by condensation of the compound or group A of compounds.

Another subject of the invention is the condensation of in situ as an agent for capturing on the skin the agent C that blocks UV radiation and at least one reactive functional group F _A that is free after condensation. Or the use of group A of compounds.

Accordingly, another object of the present invention, act to block the UV radiation comprising a reactive functional group F _C capable of forming a covalent bond or physical (ionic or hydrogen) bonds by reaction with a functional group F _A Use of a compound or group of compounds _A that can exhibit in situ condensation for capture on the skin and at least one reactive functional group FA that is free after condensation.

  According to one particular form of the invention, the substance resulting from the condensation of A may be soluble in water, and the blocking agent C is a reaction of said agent C with the substance resulting from the condensation of A. Can be selected to reduce the solubility of the substance in water.

Accordingly, the present invention is a method for cosmetic treatment of skin comprising
a compound or group of compounds _A capable of exhibiting at least one reactive functional group FA that is condensed in situ and free after condensation, and
- comprising a reactive functional group F _C capable of forming a covalent bond or physical bond by reaction with a functional group F _A, cosmetic interesting compounds C
The substance resulting from the condensation of A is soluble in water, and the reaction of the compound C with the substance resulting from the condensation of A makes the substance soluble in water. The method is selected to decrease.

According to another aspect, the present invention is a method for rendering a condensate insoluble in the skin comprising:
a compound or group of compounds _A capable of exhibiting at least one reactive functional group FA that is condensed in situ and free after condensation, and
_A blocking agent C comprising a reactive functional group F _C capable of forming a covalent or physical bond by reaction with the functional group F _A
The substance resulting from the condensation of A is soluble in water, and the blocking agent C is reacted with the substance resulting from the condensation of A by reacting said compound C with water. The method is selected such that solubility is reduced.

Another subject of the present invention is the skin of the substance resulting from the condensation of a compound or group A of compounds which can exhibit at least one reactive functional group F _A which is condensed in situ and free after condensation A method for reducing the solubility in (or even making it insoluble) on or in the skin, wherein said substance is soluble in water, said method being shared by reaction with the functional group F _A Comprising the application of said cosmetically interesting compound C to said substance, comprising a reactive functional group F _C capable of forming a chemical bond which can be binding or physical, in particular ionic, A method wherein the reaction of the agent C with the substance resulting from the condensation of A is selected such that the solubility of the substance in water is reduced.

Another subject of the invention is a method for obtaining on the skin insoluble condensates exhibiting cosmetic properties,
a compound or group of compounds _A capable of exhibiting at least one reactive functional group FA that is condensed in situ and free after condensation, and
_A blocking agent C comprising a reactive functional group F _C capable of forming a covalent or physical bond by reaction with the functional group F _A
Including application to the skin,
The substance resulting from the condensation of -A is soluble in water, so that the blocking agent C is less soluble in water due to the reaction of the blocking agent C with the substance resulting from the condensation of A. The method that is selected.

The present invention also reduces the solubility of substances resulting from condensation of a compound or group A of compounds capable of condensing in situ and exhibiting at least one reactive functional group F _A free after condensation ( Furthermore it is insoluble) to the contrary, to the use of blockers C, the substance is soluble in water, blocking agent C is a covalent bond or physical bond by reaction with a functional group F _a It also relates to the use comprising a reactive functional group F _C that can be formed.

As the amount of APTES pre-applied on the skin increases, SPF increases.

  In the context of the present invention, the term “skin” refers to the skin or scalp.

  According to the present invention, the term “agent that blocks UV radiation” refers to a mechanism known per se for absorption and / or reflection and / or scattering of UV-A and / or UV-B radiation. In general, it is intended to mean any compound or any combination of compounds that can prevent or at least limit contact of said irradiation with the surface (skin, hair) to which this or these compounds are applied. Is done. In other words, these compounds can be UV-protected photoprotective organic blocking agents or inorganic pigments that scatter and / or reflect UV, and mixtures thereof.

According to a first particular embodiment, compound A is used which can be condensed in situ. In this embodiment, compound A has at least two reactive functional groups, ie, a functional group that allows compound A to condense with itself, and at least one “capture” reactive functional group F _A or a condensation. One functional group must be included which later leads to the formation of the functional group F _A.

According to a second embodiment, group A of compounds is used. This embodiment involves the use of at least two molecules that can condense with each other. In this case, according to the present invention, the molecules constituting the group of compounds allow the presence of (several) functional groups allowing the condensation of group A and the capture reactive functional group F _A after the condensation. It must contain (several) functional groups.

According to one particular embodiment, the functional group F _A is present in only one of the compounds of the group A of compounds.

  In another embodiment, the reactive functional group is present in at least two compounds of the group of compounds.

In other words, in group A of compounds composed of molecules A ₁ and A ₂ , A ₂ may not contain a capture functional group. In this case, either A ₁ represents a capture functional group or A ₁ appears at the end of the condensation reaction. Alternatively, it is possible to Compound A ₂ contains a capture function. In this case, compound A ₁ cannot contain a capture functional group.

  For illustration, the condensation of group A of compounds can be expressed as follows:

Group A of compounds comprising _two compounds: A ₁ and A ₂
-First case: A ₁ contains a capture functional group (compound F _A -A ₁ ); A ₂ does not contain condensation products:

-Second case: A ₁ and A ₂ contain capture functional groups (identical or different)
(Compound F _A -A ₁ and Compound F ' _A -A ₁ )
Condensation product:

  It will be understood that this particularly simplified schematic example is presented for purposes of illustration only and should not be construed as limiting the invention.

According to a preferred embodiment, the method according to the invention comprises:
-application to the skin of compound A capable of condensing in situ and exhibiting at least one reactive functional group F _A free after condensation, and
-Application of an agent C that blocks UV radiation, comprising a reactive functional group F _C capable of forming a covalent bond or a physical (ionic, hydrogen) bond by reaction with the functional group F _A.

Condensation and capture functional groups are described below with respect to A, which means interchangeably above compound A or group A of compounds (eg A ₁ + A ₂ ).

  One or more capture functional groups must be at least partially free after the condensation of A so that it can react with the blocking agent C. Alternatively, the one or more capture functional groups may not be present in the compound or group of compounds A or in free form, but may appear or become free at the end of the condensation. These may be, for example, primary amine functional groups that may appear after the action of naturally occurring enzymes on the skin.

Preferably, the capture functional groups that are free after condensation should be present in a ratio such that F _capt / A is greater than 0.1, preferably greater than 0.5 (F _capt and A are captures that are free after condensation. The quantity depends on the number of functional groups and the number of molecules of A, respectively). In other words, after condensation, there are at least 1 free capture functional group, preferably at least 5 free capture functional groups per 10 molecules of A.

The capture functional group F _A of the compound or group A of compounds is typically selected from amines and other nucleophilic functional groups such as hydroxyl, thiol, sulfuric acid and phosphate functional groups. Preferably, F _A is an amine, preferably a primary amine.

The condensation of A can result from the reaction of a nucleophilic entity with an electrophilic entity. According to a first alternative, the condensed functional group is typically one that allows for the occurrence of binding by removal of water molecules according to the following equation:
R-OH + HO-R '→ RO-R' + H ₂ O

  In one particular embodiment, the compound used is an organosilane.

According to a second alternative, the condensation can result from the reaction of the entity by abstracting a proton from the second entity, in particular according to one of the following equations:
R-CH = CH ₂ + H-R '→ R-CH ₂ -CH ₂ -R'
as well as
R-CH = NH + H-R '→ R-CH ₂ -NH-R'

In the above equation, it is understood that R and R ′, independently of each other, represent any group of atoms and that the condensation product of _A must contain at least one free functional group F _A. .

  Preferably, the condensation is carried out according to the first alternative form described above.

  In one particular embodiment, compound A is an organosilicon compound comprising 1 to 3 silicon atoms and at least 2 hydroxyl or hydrolyzable groups per molecule. Compound A is therefore selected from organosilanes containing silicon atoms and organosiloxanes containing 2 or 3 silicon atoms, preferably 2 silicon atoms.

  According to one preferred embodiment, compound A is an organosilane. Compound A can in particular be an alkoxysilane, preferably a functionalized alkoxysilane.

Group A of compounds includes the above organosilicon compound (compound A ₁ ) and at least one other compound (compound A) such that this group comprising the organosilicon compound and compound A ₂ can be condensed in situ. It can be a mixture with ₂ ).

  Preferably, compound A (or at least one molecule of group A of compounds) has the formula:

(Where
R ₄ represents halogen or an OR ′ group or an R ′ ₁ group,
R ₅ represents halogen or an OR ′ group or an R ′ ₂ group,
R ₆ represents halogen or OR '''orR' ₃ group;
R ₁ , R ₂ , R ₃ , R ′, R ″, R ′ ″, R ′ ₁ , R ′ ₂ and R ′ ₃ are independently of each other an additional chemical group such as an acid group or an amine group. Represents a linear or branched and saturated or unsaturated hydrocarbon group, optionally having R ₁ , R ₂ , R ′, R ″, R ′ ″ means hydrogen Is possible and
(At least two of the R ₄ , R ₅ and R ₆ groups are different from the R ′ ₁ , R ′ ₂ and R ′ ₃ groups)
It corresponds to.

Preferably, R ₁ , R ₂ , R ′, R ″ and R ′ ″, R ′ ₁ , R ′ ₂ and R ′ ₃ are a C _{1 to} C ₁₂ alkyl group, a C _{6 to} C ₁₄ aryl group, C ₁ -C ₈ alkyl -C ₆ -C ₁₄ aryl group, and C ₆ -C ₁₄ aryl -C ₁ -C ₈ alkyl group; R ₃ is preferably, C ₁ -C ₁₂ alkyl, C ₆ ~ C ₁₄ aryl, C ₁ -C ₈ alkyl-C ₆ -C ₁₄ aryl and C ₆ -C ₁₄ aryl-C ₁ -C ₈ alkyl groups.

  Preferred organosiloxanes in the compositions of the present invention have the formula:

(Where
R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are defined as above,
R ′ ₄ represents a halogen (fluorine, bromine, chlorine or iodine) or an OR ₁₁ group,
R ₇ represents halogen or OR ₁₀ or R '' ₁ group;
R ₉ represents halogen or OR ₈ , R '' ₂ or R ₃ NR ₁ R ₂ group,
_{R '' 1, R ''} 2, R 8, R 10 and R _11, have additional chemical groups such as basic solubilizing groups optionally linear or branched and saturated or unsaturated Represents a hydrocarbon group,
(R ₁₁ , R ₁₀ and R ₈ can further mean hydrogen)
Can be represented by

Preferably, R '' ₁ , R '' ₂ , R ₈ or R ₁₀ and R ₁₁ are C ₁ -C ₁₂ alkyl groups, C ₆ -C ₁₄ aryl groups, C ₁ -C ₈ alkyl-C ₆ -C _{A 14} aryl group and a C ₆ -C ₁₄ aryl-C ₁ -C ₈ alkyl group;

At least one of the R ₆ , R ₇ and R ₉ groups means halogen or an OR ′ ″, OR ₁₀ or OR ₈ group.

  Preferably the halogen is chlorine.

  A particularly preferred class of organosilicon compounds is of the formula:

Wherein the same or different R groups are selected from C ₁ -C ₆ alkyl groups such as methyl, ethyl, propyl and butyl, and n is an integer from 1 to 6, preferably from 2 to 4. It is comprised with the compound of this.

  In particular, compound A is an alkoxysilane containing at least one nucleophilic capture functional group, in particular γ-aminopropyltriethoxysilane, known as APTES in the continuation of this text, or one of its derivatives.

Compound A ₂ which may contain in the process according to the present invention, when the group A compounds are applied to the skin, for example, may correspond to the same definition as the compound A shown in the above. Compound A _2, in particular, it can be selected from molecules having the ability to form Si-O-Si bonds. For illustration, methyltriethoxysilane (MTES) can be mentioned.

  A is chosen so that condensation occurs only when the region where this condensation must occur is reached. For example, Compound A may be highly reactive and the condensation may occur on the skin surface. Alternatively, condensation may occur if Compound A penetrates the skin to a greater or lesser extent.

Compound as chemical functional groups F _C which may be at least one reaction of the free capture functional group of the substance resulting from the condensation of the group A or the compound of A, carbonyl, carboxylic acid, sulfonic acid, ester, amine and hydroxyl functional Particular mention may be made of groups.

According to a particularly preferred form of the present invention, in order to enhance the resistance of the trapping substances formed on the skin (resistance to friction, water, sweat, sebum etc.) A mixture of the compounds A ₁ and A ₂ is used, in particular a mixture composed of γ-aminopropyltriethoxysilane (APTES) and methyltriethoxysilane (MTES). The weight ratio of A ₁ to A ₂ preferably varies from 10/90 to 90/10, more preferably from 30/70 to 70/30.

Blocking agent The blocking agent according to the invention is selected from organic UV blocking agents, inorganic blocking agents or mixtures thereof.

  Organic UV blockers include, among others, cinnamic acid derivatives; anthranilate; salicylic acid derivatives; dibenzoylmethane derivatives, camphor derivatives; hydroxyphenylbenzophenone derivatives; β, β-diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; Malonate derivatives, especially those mentioned in patent US5624663; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives described in patents EP669323 and US2463264; p-aminobenzoic acid (PABA) derivatives; patent applications US5237071, US5166355, Methylene bis (hydroxyphenylbenzotriazole) derivatives described in GB2303549, DE19726184 and EP893119; benzoxazole derivatives described in patent applications EP0832642, EP1027883, EP1300137 and DE 10162844; especially described in patent application WO93 / 04665 Shielding polymers and silicones such as those described above; α-alkylstyrene-based dimers such as those described in patent application DE19855649; described in patent applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981 4,4-diarylbutadienes such as those described; merocyanine derivatives such as those described in patent applications WO04 / 006878, WO05 / 058269 and WO06 / 032741; and mixtures thereof.

Examples of additional organic photoprotective agents include those listed below under the INCI name.
Cinnamic acid derivatives:
In particular ethylhexyl methoxycinnamate sold under the trade name Parsol MCX by DSM Nutritional Products,
Isopropyl methoxycinnamate,
Isoamylmethoxycinnamate, sold under the trade name Neo Heliopan E1000 by Symrise,
DEA-methoxycinnamate,
Diisopropylmethylcinnamate,
Glyceryl ethyl hexanoate dimethoxycinnamate.
Dibenzoylmethane derivatives:
Butyl methoxydibenzoyl methane sold under the trade name Parsol 1789, in particular by DSM
Isopropyldibenzoylmethane.
Para-aminobenzoic acid derivatives:
PABA,
Ethyl PABA,
Ethyldihydroxypropyl PABA,
Especially ethylhexyl dimethyl PABA, sold under the name Escalol507 by ISP,
Glyceryl PABA,
PEG-25 PABA sold under the name Uvinul P25 by BASF.
Salicylic acid derivatives:
Homosalate sold under the name Eusolex HMS by Rona / EM Industries,
Ethylhexyl salicylate, sold under the name Neo Heliopan OS by Symrise,
Dipropylene glycol salicylate, sold under the name Dipsal by Scher,
TEA salicylate sold under the name Neo Heliopan TS by Symrise.
β, β-diphenyl acrylate derivatives:
Octocrylene, sold under the trade name Uvinul N539, in particular by BASF
In particular, etokurylene sold under the trade name Uvinul N35 by BASF.
Hydroxyphenylbenzophenone derivative:
Benzophenone-1, sold under the trade name Uvinul400 by BASF
Benzophenone-2, sold under the trade name Uvinul D50 by BASF
Benzophenone-3 or oxybenzone sold under the trade name Uvinul M40 by BASF
Benzophenone-4, sold under the trade name Uvinul MS40 by BASF
Benzophenone-5,
Benzophenone-6, sold by Norquay under the trade name Helisorb11
Benzophenone-8, sold by American Cyanamid under the trade name Spectra-Sorb UV-24,
Benzophenone-9, sold under the trade name Uvinul DS-49 by BASF
Benzophenone-12,
N-Hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate sold under the trade name Uvinul A + by the BASF company or in the form of a mixture with octylmethoxycinnamate under the trade name Uvinul A + B.
Benzylidene camphor derivatives:
3-benzylidene camphor, manufactured under the name Mexoryl SD by Chimex
4-methylbenzylidene camphor, sold under the name Eusolex 6300 by Merck
Benzylidene camphorsulfonic acid, manufactured under the name Mexoryl SL by Chimex
Camphor benzalkonium methosulphate, manufactured by Chimex under the name Mexoryl SO
Terephthalylidene dicamphorsulfonic acid, manufactured under the name Mexoryl SX by Chimex
Polyacrylamide methylbenzylidene camphor manufactured by Chimex under the name Mexoryl SW.
Phenylbenzimidazole derivatives:
Phenylbenzimidazole sulfonic acid sold under the trade name Eusolex 232, in particular by Merck
Disodium phenyldibenzimidazole tetrasulfonate sold under the trade name Neo Heliopan AP by Symrise.
Phenylbenzotriazole derivatives:
Drometrizole trisiloxane sold under the name Silatrizole by Rhodia Chimie
Methylenebis-benzotriazolyltetra, sold in solid form under the trade name Mixxim BB / 100 by Fairmount Chemical, or sold as an aqueous dispersion in micronized form under the trade name Tinosorb M by Ciba Specialty Chemicals Methyl butylphenol.
Triazine derivatives:
Bis-ethylhexyloxyphenol methoxyphenyl triazine sold under the trade name Tinosorb S by Ciba Geigy
Ethylhexyl triazone sold under the trade name Uvinul T150, in particular by BASF
Diethylhexylbutamide triazone sold under the trade name Uvasorb HEB by Sigma3V,
2,4-Bis (n-butyl 4'-aminobenzalmalonate) -6-[(3- {1,3,3,3-tetramethyl-1-[(trimethylsilyl) oxy] disiloxanyl} propyl) amino ] -s-triazine,
2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
2,4,6-tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine,
2,4-bis (dineopentyl 4′-aminobenzalmalonate) -6- (n-butyl 4′-aminobenzoate) -s-triazine,
Patent US6225467, patent application WO2004 / 085412 (see compounds 6 and 9) or literature `` Symmetrical Triazine Derivatives '' IP.COM Journal, IP.COM INC West Henrietta, NY, US (September 20, 2004) Symmetrical triazine blockers, especially 2,4,6-tris (biphenyl) -1,3,5-triazine (especially 2,4,6-tris (biphenyl-4-yl-1,3,5-triazine) and 2,4,6-tris (terphenyl) -1,3,5-triazine (see also Beiersdorf patent applications WO06 / 035000, WO06 / 034982, WO06 / 034991, WO06 / 035007, WO2006 / 034992 and WO2006 / 034985) Have been).
Anthranilic acid derivatives:
Menthyl anthranilate sold under the trade name Neo Heliopan MA by Symrise.
Imidazoline derivatives:
Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.
Benzalmalonate derivatives:
A polyorganosiloxane containing benzalmalonate functionality, for example Polysilicone-15 sold under the trade name Parsol SLX by DSM Nutritional Products.
4,4-Diarylbutadiene derivatives:
-1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.
Benzoxazole derivatives:
2,4-bis [4- [5- (1,1-dimethylpropyl) benzoxazol-2-yl] phenylimino] -6-[(2-ethylhexyl) imino sold under the name Uvasorb K2A by Sigma3V ] -1,3,5-triazine,
And mixtures thereof.

The preferred organic blocking agent is selected from:
Ethylhexyl methoxycinnamate,
Ethylhexyl salicylate,
Homosalate,
Butylmethoxydibenzoylmethane,
Octocrylene,
Phenylbenzimidazolesulfonic acid,
Benzophenone-3,
Benzophenone-4,
Benzophenone-5,
n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate,
4-methylbenzylidene camphor,
Terephthalylidene dicamphor sulfonic acid,
Disodium phenyldibenzimidazole tetrasulfonate,
Methylene bis-benzotriazolyl tetramethylbutylphenol,
Bis-ethylhexyloxyphenylmethoxyphenyltriazine ethylhexyltriazone,
Diethylhexylbutamide triazone,
2,4,6-tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine,
2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
2,4-bis (dineopentyl 4′-aminobenzalmalonate) -6- (n-butyl 4′-aminobenzoate) -s-triazine,
2,4,6-tris (biphenyl-4-yl) -1,3,5-triazine,
2,4,6-tris (terphenyl) -1,3,5-triazine,
Drometrizol Trisiloxane Polysilicone-15,
1,1-dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene.
2,4-bis [4- [5- (1,1-dimethylpropyl) benzoxazol-2-yl] phenylimino] -6-[(2-ethylhexyl) imino] -1,3,5-triazine,
And mixtures thereof.

  The inorganic UV blocker used according to the present invention is a metal oxide pigment. More preferentially, the inorganic UV blocker of the present invention is 500 nm or less, more preferentially between 5 nm and 500 nm, even more preferentially between 10 nm and 100 nm, preferentially between 15 and 50 nm. A metal oxide pigment having an average basic particle size of

  These can in particular be chosen from titanium oxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide, or mixtures thereof.

  Such coated or uncoated metal oxide pigments are described in particular in patent application EP-A-0518773. Commercial pigments that may be mentioned include products sold by Kemira, Tayca, Merck and Degussa.

  The metal oxide pigment may be coated or uncoated.

  Coated pigments include amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylene metal alkoxides (titanium or aluminum), silicones, proteins (collagen) , Elastin), alkanolamines, silicon oxides, metal oxides or pigments that have undergone one or more surface treatments of chemical, electronic, mechanochemical and / or mechanical properties with compounds such as sodium hexametaphosphate. is there.

The coated pigment is more particularly the following coated titanium oxide:
-Titanium oxide coated with silica, for example, Sunveil from Ikeda Bussan Co., Ltd
-Titanium oxide coated with silica and iron oxide, for example the product Sunveil F from Ikeda Bussan Co., Ltd.
-Titanium oxide coated with silica and alumina, for example, the product Microtitanium Dioxide MT500SA and Microtitanium Dioxide MT100SA from Teika, and the product Tioveil from Tioxide,
-Titanium oxide coated with alumina, for example the products Tipaque TTO-55 (B) and Tipaque TTO-55 (A) from Ishihara Sangyo Co., Ltd. and the product UVT14 / 4 from Kemira,
-Titanium oxide coated with alumina and aluminum stearate, e.g. Teica products Microtitanium Dioxide MT100T, MT100TX, MT100Z and MT-01, Uniqema products Solaveil CT-10W and Solaveil CT100, Merck products Eusolex T- AVO,
-Titanium oxide coated with silica, alumina and alginic acid, for example the product MT-100AQ from Teika Co., Ltd.
-Titanium oxide coated with alumina and aluminum laurate, for example, Microtitanium Dioxide MT100S, a product of Teika Corporation
-Titanium oxide coated with iron oxide and iron stearate, for example the product Microtitanium Dioxide MT100F from Teika Co., Ltd.
-Titanium oxide coated with zinc oxide and zinc stearate, for example the product BR351 from Teika Co., Ltd.
-Titanium oxide coated with silica and alumina and treated with silicone, for example, the product Microtitanium Dioxide MT600SAS, Microtitanium Dioxide MT500SAS or Microtitanium Dioxide MT100SAS, manufactured by Teika Co., Ltd.
-Titanium oxide coated with silica, alumina and aluminum stearate and siliconized, for example, product STT-30-DS of Titanium Industry Co., Ltd.
-Titanium oxide coated with silica and treated with silicone, for example Kemira product UV-Titan X195,
-Titanium oxide coated with alumina and siliconized, for example, product Tipaque TTO-55 (S) from Ishihara Sangyo Co., Ltd. or product UV Titan M262 from Kemira,
-Titanium oxide coated with triethanolamine, for example, product STT-65-S from Titanium Industry Co., Ltd.
-Titanium oxide coated with stearic acid, for example the product Tipaque TTO-55 (C) from Ishihara Sangyo Co., Ltd.
-Titanium oxide coated with sodium hexametaphosphate, for example the product Microtitanium Dioxide MT150W from Teika Corporation.
TiO ₂ treated with octyltrimethylsilane sold under the trade name T805 by the company Degussa Silices,
-TiO ₂ treated with polydimethylsiloxane sold by the company Cardre under the trade name 70250Cardre UF TiO2SI3,
-Anatase / rutile TiO ₂ treated with polydimethylhydrogensiloxane sold by Color Techniques under the trade name Microtitanium Dioxide USP Grade Hydrophobic.

  Uncoated titanium oxide pigments are, for example, trade names Microtitanium Dioxide MT500B or Microtitanium Dioxide MT600B by Teika Corporation, P25 by Degussa, Transparent titanium oxide PW by Wacker, and UFTR by Miyoshi Kasei. It is marketed under the name Tomen by ITS and Tioxide by Tioveil AQ.

Uncoated zinc oxide pigments are, for example:
-Sold by Sunsmart under the name Z-Cote;
-Sold under the name Nanox by Elementis;
-Sold under the name Nanogard WCD2025 by Nanophase Technologies.

Coated zinc oxide pigments are, for example:
-Sold under the name Zinc Oxide CS-5 by the company Toshibi (ZnO coated with polymethylhydrogensiloxane);
-Sold under the name Nanogard Zinc Oxide FN by the company Nanophase Technologies (Finsolv TN, as a 40% dispersion in C12-C15 alkylbenzoates);
-Sold by Daito Kasei Co., Ltd. under the names `` Daitopersion ZN-30 '' and `` Daitopersion ZN-50 '' (containing 30% or 50% of nano zinc oxide coated with silica and polymethylhydrogensiloxane, Cyclopolymethylsiloxane / oxyethylenated polydimethylsiloxane dispersion);
-Sold under the name "NFD Ultrafine ZnO" by Daikin (ZnO coated with a copolymer based on perfluoroalkyl phosphate and perfluoroalkylethyl as a dispersion in cyclopentasiloxane);
-Sold under the name SPD-Z1 by Shin-Etsu Chemical Co., Ltd. (ZnO coated with a silicone grafted acrylic polymer dispersed in cyclodimethylsiloxane);
Sold under the name Escalol Z100 by the company ISP (alumina-treated ZnO dispersed in an ethylhexylmethoxycinnamate / PVP-hexadecene / methicone copolymer mixture);
-Sold under the name Fuji ZnO-SMS-10 by Fuji Dye Co., Ltd. (ZnO coated with silica and polymethylsilsesquioxane);
-Sold under the name Nanox Gel TN by the company Elementis (ZnO dispersed at a concentration of 55% in C12-C15 alkylbenzoates containing hydroxystearic acid polycondensates).

  Uncoated cerium oxide pigments are sold under the name Colloidal Cerium Oxide by the company Rhone-Poulenc.

  Uncoated iron oxide pigments are sold, for example, under the names Nanogard WCD2002 (FE45B), Nanogard Iron FE45BL AQ, Nanogard FE45R AQ and Nanogard WCD2006 (FE45R) by Arnaud or under the name TY-220 by Mitsubishi. .

  Coated iron oxide pigments are sold, for example, under the names Nanogard WCD2008 (FE45B FN), Nanogard WCD2009 (FE45B556), Nanogard FE45BL345 and Nanogard FE45BL by Arnaud or under the name Transparent Iron Oxide by BASF.

  In addition, a mixture of metal oxides, in particular a mixture of titanium dioxide and cerium dioxide, for example, a silica-coated weight-weight mixture of silica-coated titanium dioxide and silica-coated cerium dioxide sold under the name Sunveil A by Ikeda Bussan Co., Ltd. , And alumina, silica and silicone coating mixtures of titanium dioxide and zinc dioxide, such as the product M261 sold by Kemira, or alumina, silica and glycerol coating mixtures of titanium dioxide and zinc dioxide, such as by Kemira. Mention may be made of the product M211 being sold.

  According to the invention, coated or uncoated titanium oxide pigments are particularly preferred.

  In a preferred form of the invention, the blocking agent is water-soluble or water-dispersible and is generally selected from organic blocking agents that exhibit one or more anionic, preferably sulfonic or carboxylic acid functional groups. It is.

  In the continuation of this specification, a “water-soluble or water-dispersible UV blocker” is either completely dissolved in the molecular state in the aqueous phase of the composition, or otherwise in colloidal form in the aqueous phase of the composition. Is understood to mean any agent that blocks UV radiation that can be dissolved in (eg, in micellar form).

  Contemplated UV blockers preferably comprise a chromophore such as 4-aminobenzoic acid (PABA), ferulic acid, cinnamic acid, salicylic acid, benzimidazole, benzylidene camphor or benzophenone.

For example, the following can be mentioned:
PABA,
Glyceryl PABA,
PEG-25 PABA
TEA salicylate
DEA-methoxycinnamate,
Benzophenone-4, sold by BASF under the trade name `` Uvinul MS40 '',
Benzophenone-5,
Benzophenone-12,
Phenylbenzimidazolesulfonic acid,
Benzylidene camphorsulfonic acid camphorbenzalkonium methosulphate,
Terephthalylidene dicamphor sulfonic acid,
Disodium phenyldibenzimidazole tetrasulfonate.

More preferably,
Phenylbenzimidazolesulfonic acid,
Terephthalylidene dicamphor sulfonic acid,
Disodium phenyldibenzimidazole tetrasulfonate or a mixture thereof is used.

According to one preferred embodiment, the method of the invention comprises:
-application to the skin of compound A capable of condensing in situ and exhibiting at least one reactive functional group F _A free after condensation, and
- including the application of ionic (in particular carboxylic acid or sulfonic acid) soluble containing reactive functional groups F _C capable of forming a bond or a water-dispersible UV filters by reaction with a functional group F _A.

  The blocking agent is generally in the range from 0.1% to 15% by weight, preferably from 0.2% to 10%, more preferentially from 1% to 6% by weight relative to the total weight of the composition. Present in proportion.

  Compound A (or group of compounds A) and blocking agent C are selected according to one or more properties that it is desired to apply on the skin.

  The method according to the invention involves the application to the skin of a compound or group A of compounds which can condense, in particular when it is exposed to the increased concentration obtained by evaporation of the medium in which it is present. The compound or group of compounds A thus contains a reactive functional group to allow this condensation, as mentioned above.

  This condensation results in the formation of a deposited layer on the skin. This deposited layer is not necessarily continuous, but may consist of a number of linked domains. Compound A is selected such that the material resulting from the condensation exhibits a free reactive functional group referred to as a “trapping functional group”.

  Blocker C is also applied to the skin.

The blocking agent C can react with the condensation product of A via the capture functional group F _A that is free after condensation and the functional group F _C present in the blocking agent C.

  The method according to the invention involves the sequential application of blocking agent C.

  In one embodiment of the invention, in the first step, compound A (or group of compounds A) is applied to the skin area. Thereafter, it can be between 1 minute and 5 hours, preferably between 1 minute and 1 hour, more preferably between 2 minutes and 10 minutes. Applies to the same area.

  In the context of this embodiment, the condensation of compound A (or of group A of compounds) can occur spontaneously or may have been induced prior to application of blocking agent C. The blocking agent C can then react with the condensate via one or more free capture functional groups in the condensate. Blocker C may also be able to participate in the reaction of one or more reactive functional groups other than the capture functional group with A, in particular, A itself, but did not react. Can also react with groups.

  Thus, it is understood that in the specific case where compound A is an organosilane bearing a capture functional group, the blocking agent C can react with the capture functional group of the condensate and uncondensed silanol.

The chemical reaction is then shared between the blocking agent C and one or more reactive functional groups, more particularly with the capture functional group F _A present in the condensate of compound A or group A of compounds. It occurs with the formation of bonds or physical bonds. This can have the effect of modifying the substance on the skin. This reaction can in particular make the condensate insoluble while maintaining the blocking properties conferred by blocking agent C, and even further strengthening, and therefore its persistence on and / or in the skin. (Resistance to water, sweat, sebum, etc.) can be further increased.

  The present invention can be used in conjunction with methods of accelerating or suppressing the reactions performed in the present invention, such as heat or cold, microwaves, pH agents or catalysts.

  It is also possible to act on the reaction between the blocking agent C and the compound or group A of compounds from the surface of the skin, for example to modulate the reaction or to make the reaction faster.

  According to an alternative form of the process according to the invention, compound A is first applied and then there is a waiting time until the reaction for the condensation of A occurs. This may be rapid or slow, may or may not involve drying the skin, or with or without activation, for example by use of a heat source or another energy source May be. At this stage, it is possible to apply blocking agent C, or to rinse and then to apply blocking agent C. Blocker C can remain reacted with the material resulting from the condensation of A. It is also possible to activate the reaction between A and C. After the reaction between A and C, rinsing may or may not be performed.

  According to one particular embodiment, compound A is applied in a form or under conditions that do not allow a condensation reaction. There is a waiting time for Compound A to penetrate. The reaction is then elicited by either adding an adjuvant (eg, a pH agent) or changing the conditions, for example by changing the temperature (especially by increasing the temperature). Once the condensation has started and optionally after the rinsing step, the blocking agent C is applied as described above.

  In another alternative, Compound A or Group A of compounds is applied, and then Blocker C is applied under conditions where no capture reaction can occur. Condensation occurs. When condensation starts, the reaction of blocking agent C with the condensate of A is triggered.

  In one particular embodiment, compounds A and C are mixed prior to application to the skin (mixed in use). This mixing can take place before application or during application to the skin (direct mixing on the area of the skin to be treated).

Compound A (or group of compounds A) and blocking agent C can therefore be applied in combination. In this case,
The compound A and the blocking agent C are selected such that the presence of C does not prevent the condensation of A, or
The compound A and the blocking agent C and / or the conditions of use are chosen such that the condensation of A is faster than the reaction of C, or
-Blocker C cannot react, but compound A can condense. After a while, the reaction of the blocking agent C is triggered by subsequent action or naturally, for example by a change in pH or temperature or by application of a light source.

  In one particular embodiment, the result of the condensation of A is applied to the skin. For example, a poly APTES thin film can be applied. Blocking agent C is subsequently applied.

  In another embodiment, blocking agent C is applied first, followed by compound A.

  In general, the reaction can be accelerated by the use of suitable catalysts such as pH agents, salts, metals and / or enzymes.

  Another subject of the invention is a cosmetic composition comprising an effective amount of a compound A that can be condensed in situ on the skin, and an effective amount of one or more substances resulting from the condensation of compound A or The combined use of a cosmetic composition comprising a blocking agent C that will react with further free reactive functional groups.

Formulation Form Compound A, or group of compounds A, and blocking agent C can be formulated in a composition comprising a physiologically acceptable medium.

  These compositions can be provided according to any formulation form conventionally used in the envisaged application. Of course, one skilled in the art will recognize that the components and optional components are such that the contemplated additions have no or substantially no adverse effect on the advantageous properties of Compound A (or Compound Group A) and Blocker C. Carefully select additional ingredients and / or active agents and / or amounts thereof.

  In one particular embodiment, the composition used according to the invention is an aqueous composition.

  Compositions containing the blocking agent C used for photoprotection of the skin can be prepared according to techniques well known to those skilled in the art. It should be noted that the formulation forms and active agents described below can be used in the formulation of Compound A.

  The compositions used according to the invention are in particular fatty substances, organic solvents, ionic or non-ionic, hydrophilic or lipophilic thickeners, softeners, wetting agents, opacifiers, stabilizers, emollients. , Silicone, antifoaming agent, fragrance, preservative, anionic, cationic, nonionic, zwitterionic or amphoteric surfactant, activator, filler, polymer, propellant, acidifying agent or basifying agent Alternatively, standard cosmetic auxiliaries selected from any other ingredients commonly used in cosmetics and / or in dermatology can be included. These cosmetic adjuvants can be incorporated interchangeably in compositions containing A, in compositions containing blocking agent C, or in both compositions.

  The fatty substance may consist of oil or a wax other than the nonpolar wax as defined above or a mixture thereof. The term oil means a compound that is liquid at room temperature. The term wax means a compound that is solid or substantially solid at room temperature and has a melting point generally above 35 ° C.

  Oils that may be mentioned are mineral oils (paraffin); vegetable oils (sweet tonsil oil, macadamia oil, black currant oil or jojoba oil); synthetic oils such as perhydrosqualene, fatty alcohols, fatty amides (e.g. Eldew SL-205 Lauroyl sarcosine isopropyl sold by Ajinomoto Co., Inc.), fatty acids or fatty esters, for example, 2-ethylphenylbenzoate such as C12-C15 alkyl benzoate sold by Witco under the trade name Finsolv TN or Witconol TN For example, a commercially available product sold by ISP under the name X-Tend226 (registered trademark), octyl palmitate, isopropyl lanolate, diisopropyl sebacate sold by Steininerie Dubois under the name Dub Dis, Triglycerides (including capric / caprylic triglycerides), and Cetiol CC Dicaprylyl carbonate, oxyethylenated or oxypropylenated fatty esters and ethers sold by the company Cognis by name; silicone oils (cyclomethicone and polydimethylsiloxane, or PDMS) or fluoro oils, polyalkylenes and trialkyl trimelli Tate, such as tridecyl trimellitate.

  Wax compounds that may be mentioned include carnauba wax, beeswax, hydrogenated castor oil, polyethylene wax and polymethylene wax, for example the wax sold under the name Cirebelle 303 by the company Sasol.

  Examples of the organic solvent include lower alcohols and polyols. Such polyols can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

  Hydrophilic thickeners that may be mentioned are carboxyvinyl polymers, such as Carbopol (Carbomer) and Pemulen (acrylate / C10-C30 alkyl acrylate copolymer); polyacrylamides such as Sepigel 305 (CTFA name: Polyacrylamide / C13- 14 Isoparaffin / Laureth7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyl dimethyl taurate copolymer / isohexadecane / polysorbate 80) etc. 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, such as poly (2-acrylamido-2-methyl) sold by Clariant under the trade name Hostacerin AMPS (CTFA name: ammonium polyacryloyldimethyltaurate) Propanesulfonic acid) or Simulgel 800 (CTFA name: sodium polyacryloyl dimethyl taurate / polysorbate 80 / sorbitan oleate) sold by SEPPIC, etc .; copolymer of 2-acrylamido-2-methylpropane sulfonic acid and copolymer of hydroxyethyl acrylate, such as SEPPIC Simulgel NS and Sepinov EMT10 sold by the company; Cellulose derivatives such as hydroxyethyl cellulose; polysaccharides and especially gums such as xanthan gum; water-soluble or water-dispersible silicone derivatives such as acrylic silicones, polyether silicones and cationic Including silicone and the like, as well as mixtures thereof.

  Lipophilic thickeners that may be mentioned are synthetic polymers such as poly (C10-C30 alkyl acrylates) sold by the company Landec under the names Intelimer IPA13-1 and Intelimer IPA13-6, or modified clays such as Hectorite and derivatives thereof, for example, products sold under the name Bentone.

  Of course, those skilled in the art will recognize that these optional additional compounds and / or such that the contemplated additions have no or substantially no adverse effect on the advantageous properties inherent in the compositions used according to the invention. Or the amount will be carefully selected.

  Compositions used for skin photoprotection or care according to the present invention, and compositions comprising Compound A or Group A of compounds can be prepared according to techniques well known to those skilled in the art. These are in particular in the form of simple or complex emulsions (O / W, W / O, O / W / O or W / O / W) such as creams, emulsions or cream-gels; in the form of aqueous or oily gels; It can be in the form. These may optionally be packaged in an aerosol form and may be in the form of a mousse or spray.

  The composition used according to the invention is preferably in the form of an oil-in-water or water-in-oil emulsion, or in the form of an aqueous gel.

  The emulsification process that can be used is of the paddle or propeller, rotor-stator or HPH type.

  It is also possible to obtain a stable dispersion with a droplet size that can be as small as 100 nm with HHP (50-800 bar).

  Emulsions generally contain at least one emulsifier selected from amphoteric, anionic, cationic or nonionic emulsifiers used alone or as a mixture. The emulsifier is appropriately selected depending on the emulsion to be obtained (W / O or O / W).

  Examples of emulsifying surfactants that can be used in the preparation of W / O emulsions include sorbitan, glycerol or alkyl esters or ethers of sugars; silicone surfactants such as dimethicone copolyols such as DC5225C by Dow Corning. Mixtures of cyclomethicone and dimethicone copolyol sold under the name, and alkyl dimethicone copolyols, such as lauryl methicone copolyol sold under the name Dow Corning 5200 Formulation Aid by Dow Corning; cetyl dimethicone Copolyols, for example products sold under the name Abil EM90R by the company Goldschmidt and cetyl dimethicone copolyol and polyglyceryl isostearate (4 mol) and hexyl laurate sold under the name Abil WE O9 by the company Goldschmidt A mixture with be able to. It is also possible to add to this one or more co-emulsifiers which can advantageously be selected from the group comprising polyol alkyl esters.

  As polyol alkyl esters, mention may be made in particular of polyethylene glycol esters, for example PEG-30 dipolyhydroxystearate, for example the product sold under the name Arlacel P135 by the company ICI.

  Glycerol and / or sorbitan esters that may be mentioned are, for example, polyglyceryl isostearate, for example the product sold under the name Isolan GI34 by the company Goldschmidt, sorbitan isostearate, for example sold under the name Arlacel987 by the company ICI. Products, sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.

  For O / W emulsions, examples of emulsifiers that may be mentioned are nonionic emulsifiers, such as oxyalkylenated (more specifically polyoxyethylenated) esters of fatty acids and glycerol; oxyalkylenated fatty acids and sorbitan Esters; oxyalkylenated (oxyethylenated and / or oxypropylenated) esters of fatty acids, e.g. PEG-100 stearate / glyceryl stearate mixture sold under the name Arlacel 165 by the company ICI; fatty alcohol oxy Alkyleneated (oxyethylenated and / or oxypropylenated) ethers; sugar esters, such as sucrose stearate; or ethers of fatty alcohols and sugars, especially alkyl polyglucosides (APG), such as, for example, Plantaren 2000 and Henkel respectively Plantaren1200 Decyl glucoside and lauryl glucoside sold under the name, e.g., optionally sold by SEPPIC under the name Montanov68, by Goldschmidt under the name Tegocare CG90 and by Henkel under the name Emulgade KE3302, optionally cetostearyl Cetostearyl glucoside as a mixture with alcohol and also arachidyl glucoside in the form of a mixture of arachidyl alcohol, behenyl alcohol and arachidyl glucoside, sold for example by the company SEPPIC under the name Montanov202. According to one particular embodiment of the invention, the mixture of alkylpolyglucoside as defined above and the corresponding fatty alcohol is, for example, a self-emulsifying composition described in document WO-A-92 / 06778. Form may be sufficient.

  When the composition of the present invention is an emulsion, the aqueous phase of the emulsion is determined by known methods (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965), FR2315991 and FR2416008). A prepared nonionic vesicular dispersion may be included.

  Cosmetic compositions used according to the present invention are, for example, liquid to semi-liquid consistency, facial and / or bodily care products and / or sun protection products, for example, emulsions, to a greater or lesser extent. It can be used as a cream, cream-gel or paste. These may optionally be packaged in an aerosol form and may be in the form of a mousse or spray.

  The composition according to the invention in the form of an evaporating fluid lotion according to the invention is applied to the skin or scalp in the form of fine particles by means of a pressure device. Devices according to the present invention are well known to those skilled in the art and include non-aerosol pumps or “atomizers”, aerosol containers containing a propellant, and aerosol pumps using compressed air as a propellant. These devices are described in patents US4077441 and US4850517 (these patents form part of the contents of this description).

  Compositions provided in the form of aerosols according to the present invention generally contain conventional propellants such as hydrofluoro compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane. The propellant is preferably present in an amount ranging from 15% to 50% by weight relative to the total weight of the composition.

  The compositions used according to the invention can also additionally contain additional cosmetic or dermatological active agents.

Activators can include the following:
-Vitamins (A, C, E, K, PP, etc.) and their derivatives or precursors, alone or as a mixture;
-An anti-glycation agent;
-Sedatives;
-NO-synthase inhibitors;
-Agents that stimulate the synthesis of dermal or epidermal macromolecules and / or prevent their degradation;
-Agents that stimulate fibroblast proliferation;
-Agents that stimulate keratinocyte proliferation;
-Muscle relaxants;
-Tensioning agent;
-Matting agent;
-Keratolytic agents;
-Desquamating agent;
A moisturizer, for example a polyol such as glycerol, butylene glycol or propylene glycol;
-Anti-inflammatory agents;
-Agents that affect cellular energy metabolism;
-Insect repellent;
-Substance P or CGRP antagonist;
-Hair-loss counteractant and / or hair restorer;
-Antidepressants.

  Of course, those skilled in the art will appreciate that the optional additional compounds described above and / or their additions so that the envisaged addition does not have any or substantially adverse effects on the advantageous properties inherently associated with the composition according to the invention. The amount will be chosen carefully.

  One skilled in the art will select the active agent according to the desired effect on the skin.

  The composition also provides a natural coloring of the filler or skin with a soft focus effect aimed at complementing the biological effects of these active agents or providing an immediate visual anti-aging effect. It can further comprise at least one component, such as a stimulating agent.

  For the care and / or makeup of oily skin, the person skilled in the art preferably uses at least one active agent selected from desquamating agents, sebum regulators or anti-seborrhoeic agents and astringents. Will choose.

  The compositions used according to the invention can also contain at least one additional ingredient to complement the biological effects of these active agents or to give a fast-acting visual effect, in particular matting agents. Mention may be made of soft focus fillers, fluorescent agents, agents for promoting the natural pinkish coloring of the skin, and abrasive fillers or exfoliants.

  In order to complement and / or optimize the effect of the above-mentioned cosmetic and / or dermatological active agents on keratin materials, it may be advantageous to incorporate other additional ingredients into the composition of the present invention.

  In particular, these additional components can provide an immediate visual effect that is relayed by the biological effects of the active agents described above. They can also amplify the effects of the bioactive agents described above by mechanical action (eg, abrasive fillers).

Matting agent The term “matting agent” means an agent intended to make the skin more visually matt and less glossy.

  The matting effect of the matting agent and / or the composition containing it can be evaluated in particular by measuring the ratio R between specular reflection and irregular reflection using a gonioreflectometer. An R value of 2 or less generally indicates a matte effect.

  Matting agents are in particular rice starch or corn starch (INCI name: Zea Mays (Corn) Starch, e.g. the product sold under the trade name Farmal CS3650PlUS036500, in particular by National Starch), kaolinite, talc, pumpkin seed extract, cellulose Coated with microbeads, plant fibers, synthetic fibers, especially polyamide fibers, foamed acrylic copolymer microspheres, polyamide powder, silica powder, polytetrafluoroethylene powder, silicone resin powder, acrylic polymer powder, wax powder, polyethylene powder, silicone resin Selected from elastomeric crosslinked organopolysiloxane powders, talc / titanium dioxide / alumina / silica composite powders, amorphous mixed silicate powders, silicate particles, in particular mixed silicate particles, and mixtures thereof.

As examples of matting agents, mention may in particular be made of:
-Rice or corn starch, in particular aluminum starch octenyl succinate sold under the name Dry Flo® by the company National Starch;
-Kaolinite;
-silica;
-talc;
-Pumpkin seed extract sold under the name Curbilene® by the company Indena;
-Cellulose microbeads described in patent application EP1562562;
-Fibers such as silk fibers, cotton fibers, wool fibers, flax fibers, especially cellulose fibers extracted from wood, plants or algae, polyamide (Nylon®) fibers, modified cellulose fibers, poly-p-phenylene tele Phthalamide fiber, acrylic fiber, polyolefin fiber, glass fiber, silica fiber, aramid fiber, carbon fiber, Teflon (registered trademark) fiber, insoluble collagen fiber, polyester fiber, polyvinyl chloride or polyvinylidene chloride fiber, polyvinyl alcohol fiber, poly Acrylonitrile fibers, chitosan fibers, polyurethane fibers, polyethylene phthalate fibers, fibers formed from a mixture of polymers, resorbable synthetic fibers, and mixtures thereof (described in patent application EP1151742);
-Foamed acrylic copolymer microspheres, such as those sold by the company Expancel under the name Expancel551®;
-Fillers with optical effects (especially those described in patent application FR2869796):
-Polyamide (Nylon®) powder, for example, Orgasol type Nylon 12 particles from Arkema with an average particle size of 10 microns and a refractive index of 1.54,
-Silica powder, for example, Silica beads SB150 manufactured by Miyoshi Kasei Co., Ltd., having an average particle size of 5 microns and a refractive index of 1.45,
-Polytetrafluoroethylene powder, for example PTFE Ceridust9205F from Clariant with an average particle size of 8 microns and a refractive index of 1.36,
A silicone resin powder, for example, the silicone resin Tospearl145A from GE Silicone with an average particle size of 4.5 microns and a refractive index of 1.41;
-Acrylic copolymer powders, in particular polymethyl (meth) acrylate acrylic copolymer powders, for example PMMA particles Jurymer MBI from Nihon Junyoki with an average particle size of 8 microns and a refractive index of 1.49, or Micropearl M100 from Matsumoto Yushi Seiyaku Co., Ltd. (Registered trademark) and F80ED (registered trademark) particles,
-Wax powder, for example, paraffin wax particles Microease114S from Micropowders with an average particle size of 7 microns and a refractive index of 1.54,
-Polyethylene powders, in particular those comprising at least one ethylene / acrylic acid copolymer, in particular those consisting of ethylene / acrylic acid copolymers, for example Flobaads EA209 particles from Sumitomo (average particle size 10 microns and refractive index 1.48),
-Elastomeric crosslinked organopolysiloxane powders coated with silicone resins, in particular silsesquioxane resins (e.g. described in patent US5538793) (such elastomer powders are manufactured by Shin-Etsu Chemical Co., Ltd. by KSP-100, KSP- 101, KSP-102, KSP-103, KSP-104 and KSP-105), and
-Talc / Titanium dioxide / Alumina / Silica composite powder, for example, sold under the name Coverleaf® AR-80 by Catalyst & Chemicals,
-Mixtures of them,
-Compounds that absorb and / or adsorb sebum as described in patent application FR2869796. In particular, the following may be mentioned:
-Silica powder, e.g. porous silica microspheres sold under the name Silica Beads SB-700 by Miyoshi Kasei Co., Ltd., Sunsphere® H51, Sunsphere® H33 and Sunsphere (registered by Asahi Glass Co., Ltd.) (Trademark) Products sold under H53, SA Sunsphere (registered trademark) H-33 sold by Asahi Glass Co., Ltd. and polydimethylsiloxane coated amorphous sold under the name SA Sunsphere (registered trademark) H-53 Silica microspheres;
Amorphous mixed silicate powders, in particular amorphous mixed silicate powders of aluminum and magnesium, for example products sold under the name Neusilin UFL2 by Sumitomo;
-Polyamide (Nylon®) powder, for example Orgasol® 4000 sold by the company Arkema, and
-Acrylic polymer powder, especially polymethyl methacrylate powder (e.g. Covabead® LH85 sold by Wackherr), polymethyl methacrylate / ethylene glycol dimethacrylate powder (e.g. Dow Corning 5640 Microsponge sold by Dow Corning) (Registered trademark) Skin Oil Adsorber or Ganzpearl (registered trademark) GMP-0820 sold by Ganz Chemical Company, polyallyl methacrylate / ethylene glycol dimethacrylate powder (e.g. Poly-Pore (registered by Amcol Company) L200 or Poly-Pore® E200), ethylene glycol dimethacrylate / lauryl methacrylate copolymer powder (for example, Polytrap® 6603 sold by Dow Corning);
-Silicate particles, e.g. alumina silicate;
-Mixed silicate particles, for example:
-Magnesium aluminum silicate particles, such as hydrated magnesium aluminum silicate containing sodium sulfate sold by Saponite or Kunimine Industry Co., Ltd. under the trade name Sumecton®;
-Magnesium silicate, hydroxyethyl cellulose, black cumin oil, mallow oil and phospholipid complex or Matipure® from Lucas Meyer, and
-A mixture of them.

  Preferred matting agents that can be used according to the present invention include pumpkin seed extract, rice or corn starch, kaolinite, silica, talc, polyamide powder, polyethylene powder, acrylic copolymer powder, foamed acrylic copolymer microspheres, silicone resin microspheres. Examples include beads and mixed silicate particles and mixtures thereof.

Fillers with a soft focus effect These fillers can be any material that can modify and hide wrinkles due to its inherent physical properties. These fillers can in particular correct wrinkles by means of a tensioning effect, a covering effect or a soft focus effect.

As examples of fillers, the following compounds can be shown:
-Porous silica fine particles, for example, Silica Beads (registered trademark) SB150 and SB700 (average particle size 5 μm) manufactured by Miyoshi Kasei Co., Ltd. and series Sunspheres (registered trademark) H manufactured by Asahi Glass Co., (Particle sizes are 3.5 and 5 μm, respectively);
Hollow hemispherical silicone resin particles, for example, NLK500 (registered trademark), NLK506 (registered trademark) and NLK510 (registered trademark) manufactured by Takemoto Yushi Co., Ltd., particularly described in EP-A-1579849;
A silicone resin powder, for example, the silicone resin Tospearl® 145A from GE Silicone (average particle size 4.5 μm);
-Acrylic copolymer powder, in particular polymethyl (meth) acrylate powder, for example PMMA particles from Nihon Junyoki Jurimer MBI® (average particle size 8 μm), sold under the name Covabead® LH85 by Wackherr PMMA hollow spheres, and vinylidene / acrylonitrile / methylene methacrylate expanded microspheres sold under the name Expancel®;
A wax powder, for example, paraffin wax particles MicroEase® 114S from MicroPowders (average particle size 7 μm);
-Polyethylene powder, in particular those comprising at least one ethylene / acrylic acid copolymer, for example Floveads® EA209E particles from Sumitomo (average particle size 10 μm);
-Crosslinked elastomeric organopolysiloxane powder coated with silicone resin, especially silsesquioxane resin (KSP-100 (registered trademark), KSP-101 (registered trademark), KSP-102 (registered by Shin-Etsu Chemical Co., Ltd.)) Trademark), KSP-103 (registered trademark), KSP-104 (registered trademark) and KSP-105 (registered trademark));
-Talc / titanium dioxide / alumina / silica composite powders, such as those sold by Catalyst & Chemicals under the name Coverleaf AR-80®;
-Starch powder cross-linked with talc, mica, kaolin, lauryl glycine, octenyl succinic anhydride, boron nitride, polytetrafluoroethylene powder, precipitated calcium carbonate, magnesium carbonate, basic magnesium carbonate, barium sulfate, hydroxyapatite, silicic acid Calcium, cerium dioxide and glass or ceramic microcapsules;
-Hydrophilic or hydrophobic, synthetic or natural, inorganic or organic fibers, e.g. silk fibers, cotton fibers, wool fibers, flax fibers, in particular cellulose fibers extracted from wood, plants or algae, polyamides (Nylon ( (Registered trademark)) fiber, modified cellulose fiber, poly-p-phenylene terephthalamide fiber, acrylic fiber, polyolefin fiber, glass fiber, silica fiber, aramid fiber, carbon fiber, polytetrafluoroethylene (Teflon (registered trademark)) fiber, Insoluble collagen fibers, polyester fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, chitosan fibers, polyurethane fibers, polyethylene phthalate fibers, fibers formed from a mixture of polymers, absorbent synthetic fibers, and Mixtures thereof (described in patent application EP1151742);
-Spherical elastomeric cross-linked silicone, for example, Trefil E-505C® or E-506C® from Dow Corning;
Abrasive fillers that flatten the macro-relief of the skin by mechanical action, for example abrasive silica, eg Abrasif SP® from Semanez or nut or shell powder (eg apricot or walnut powder from Cosmetochem).

  In particular, fillers having an effect on aging signs are porous silica fine particles, hollow hemispherical silicone particles, silicone resin powder, acrylic copolymer powder, polyethylene powder, crosslinked elastomeric organopolysiloxane powder coated with silicone resin, talc / From titanium dioxide / alumina / silica composite powder, precipitated calcium carbonate, magnesium carbonate, magnesium bicarbonate, barium sulfate, hydroxyapatite, calcium silicate, cerium dioxide, glass or ceramic microcapsules, silk fiber or cotton fiber, and mixtures thereof Selected.

  The filler may be a soft focus filler.

  The term “soft focus” filler refers to a filler that further provides a skin-colored transparency and a dull effect. Preferably, the soft focus filler has an average particle size of 15 microns or less. These particles can be in any form, in particular spherical or non-spherical. These fillers are more preferably non-spherical.

  Soft focus fillers are silica and silicate powders, especially alumina powder, polymethyl methacrylate (PMMA) type powder, talc, silica / TiO2 or silica / zinc oxide composite, polyethylene powder, starch powder, polyamide powder, styrene / It can be selected from acrylic copolymer powders and silicone elastomers, and mixtures thereof.

  In particular, talc having a number average particle size of 3 microns or less, for example, talc having a number average particle size of 1.8 microns, particularly those sold under the trade name Talc P3 (registered trademark) by Nippon Talc Co., Ltd., Nylon (registered trademark) 12 Powders, especially those sold under the name Orgasol 2002 Extra D Nat Cos (registered trademark) by the company Atochem, silica particles (INCI name: hydrated silica (and) paraffin) surface treated with mineral wax 1% -2%, For example, those sold by Degussa, amorphous silica microspheres, such as those sold under the name Sunsphere by Asahi Glass Co., Ltd. (e.g. reference symbol H-53®), and silica micro Mention may be made of beads, for example those sold by Miyoshi Kasei Co., Ltd. under the name SB-700® or SB-150®, and these listings are not limiting.

  The concentration of these fillers that have an effect on aging signs in the composition according to the invention is from 0.1% to 40% by weight, or even from 0.1% to 20% by weight, based on the total weight of the composition. can do.

Agents that promote natural pinkish coloration of the skin The compositions used according to the present invention may also comprise agents that promote the natural pinkish coloration of the skin. In particular, the following may be mentioned:
-Self-tanning agents, i.e., when applied to the skin, especially the face, produce a sunburn effect with a similar appearance, albeit to some extent, to the extent of prolonged exposure to sunlight (natural tanning) or under UV lamps Agents capable of;
-Additional colorant, i.e. it can give the skin a persistent and uncovered color (i.e. does not tend to opacify the skin) and is removed with water or with a solvent Any compound with a special affinity for the skin that is resistant to rubbing and washing with aqueous solutions containing surfactants (thus this persistent coloring is provided, for example, by makeup pigments) Distinguished from superficial and temporary coloring);
And mixtures thereof.

Examples of self-tanning agents that may be mentioned in particular include:
Dihydroxyacetone (DHA) (used as a supplement to compound C for skin photoprotection (or blocker) or care),
A combination of erythrulose and a catalyst system formed from:
Manganese and / or zinc salts and oxides and alkali metal and / or alkaline earth metal hydrogen carbonates.

  Self-tanning agents are generally monocarbonyl or polycarbonyl compounds such as isatin, alloxan, ninhydrin, glyceraldehyde, mesotartaric acid aldehyde, glutaraldehyde, erythrulose, pyrazoline-4,5-dione derivatives (patent applications FR2466492 and WO97 / 35842). ), Dihydroxyacetone (DHA), and 4,4-dihydroxypyrazolin-5-one derivatives (described in patent application EP903342). Preferably DHA is used.

  DHA may be used in free form and / or encapsulated in lipid vesicles such as, for example, liposomes described in particular in patent application WO 97/25970.

  In general, the self-tanning agent is present in an amount ranging from 0.01% to 20%, preferably from 0.1% to 10% by weight of the total weight of the composition.

  Other dyes that allow correction of the color produced by the self-tanning agent can also be used.

  These dyes can be selected from synthetic or natural direct dyes.

These dyes can be selected, for example, from fluoran red or orange dyes such as those described in patent application FR2840806. For example, the following dyes can be mentioned:
-CTFA name: tetrabromofluorescein or eosin known as CI45380 or Red21;
-CTFA name: Phloxine B, known as CI45410 or Red27;
-CTFA name: Diiodofluorescein known as CI45425 or Orange 10;
-CTFA name: dibromofluorescein known as CI45370 or Orange5;
-CTFA name: sodium salt of tetrabromofluorescein known as CI45380 (Na salt) or Red22;
-CTFA name: Phloxine B sodium salt known as CI45410 (Na salt) or Red28;
-CTFA name: diiodofluorescein sodium salt known as CI45425 (Na salt) or Orange 11;
-CTFA name: erythrocin known as CI45430 or Acid Red51;
-CTFA name: Phloxin known as CI45405 or Acid Red98;

  These dyes can also be selected from anthraquinone, caramel, carmine, carbon black, azulene blue, methoxalene, trioxalene, guaiazulene, camazulene, rose bengal, eosin 10B, cyanocin or dafinine.

  These dyes are also described in indole derivatives, such as monohydroxyindoles described in patent FR2651126 (ie: 4-, 5-, 6- or 7-hydroxyindoles) or patent EP-B-0425324 Select from dihydroxyindole (ie: 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole or 2,3-dimethyl-5,6-dihydroxyindole) be able to.

Abrasive fillers or release agents As examples of release agents that can be used in rinse-out compositions according to the invention, mention may be made of mineral, plant or organic derived release particles or scrub particles. Including. Thus, for example, polyethylene beads or powders, nylon powders, polyvinyl chloride powders, pumice powders, grounds from apricot kernels or walnut shells, sawdust, glass beads, alumina and mixtures thereof may be used. In addition, Exogreen (registered trademark) (bamboo extract) manufactured by Solabia, strawberry fruit extract (strawberry fruit manufactured by Greentech), peach seed powder or apricot powder, and finally, in the field of plant powder having a polishing effect, Mention may be made of cranberry seed powder.

  Preferred abrasive fillers or release agents according to the present invention include peach seed powder, apricot seed powder, cranberry seed powder, strawberry fruit extract or bamboo extract.

The present invention also includes at least
A first composition comprising at least one compound as described above or group A of compounds in a physiologically acceptable medium,
It also relates to a cosmetic assembly or kit comprising a second composition comprising at least one blocking agent C as described above in a physiologically acceptable medium.

  Thus, the assembly according to the invention can be constructed in a two-compartment system. This can also correspond to an assembly comprising a first composition in a first formulation form (eg a cream comprising a compound or group A of compounds) and a second composition in a second formulation form.

  The following examples are given as non-limiting illustrations in the field of the invention.

(Example)
Formulations containing alkoxysilanes with free amine functionality:

Examples of compositions containing UV blockers

  Demonstration of improved persistence against barrier and water properties

Assay principle:
The blocking effectiveness and water persistence of the UV blocker solution applied to the APTES condensed deposition layer is evaluated and compared at various concentrations compared to the solution deposited on the bare skin. The UV blocking agents tested are phenyl benzimidazole sulfonic acid and terephthalylidene dicamphor sulfonic acid.

The test was conducted on five volunteers of phototype I, II or III. If 3 days were required for the measurement of persistence against water, a trial targeted only to determine the blocking efficacy was conducted over 2 consecutive days. On the first day, the blocking formulation is applied at ² mg / cm ² on the bare skin or on the condensed layer of APTES. Volunteers are then exposed to ultraviolet radiation. Read erythema and define SPF after 24 h. In the case of a persistence test for water, the same solution or solution pair is applied on the second day. Volunteers are immersed in two successive water baths for 20 minutes each and then exposed again to UV radiation. During the third day of the test, determine the post-bath SPF. Water resistance (WR) is defined as follows:

  Equations 1 and 2 that are tested are stable after 2 months at ambient temperature and show a very good sensory quality after application to the skin.

  The equation is tested by successive application of APTES solution and then blocking solution. The various conditions tested are as follows:

  Conditions I and II were tested for SPF and water resistance.

Conditions I, II, III, IV, V and VI were tested for SPF.
I => Example 2
II => Example 2+ Example b (50/50)
III => Example 2+ Example d (50/50)
IV => Example 1
V => Example 1 + Example a (50/50)
VI => Example 1 + Example c (50/50)

  The SPF values of 8% and 12% solutions of UV blockers are measured, and this measurement is made after application on bare skin or, to a lesser extent, on a concentrated deposition layer.

  The APTES / UV blocking agent ratio corresponds to the weight ratio between APTES deposited on the skin and the UV blocking agent (Mexoryl SX + Eusolex232).

  The water resistance of a 12% solution of UV blocker was also evaluated in vivo with and without APTES. The water resistance data compared is in the table below.

  The APTES layer makes it possible to significantly increase the water resistance (which is nevertheless water soluble) of the UV blocker of Example 2.

  Similar to 12%, an 8% blocking solution of UV blocker exhibits greater SPF in vivo when applied over a deposited layer of APTES.

  In this study, the dose effect of APTES was demonstrated: SPF increases proportionally with increasing amount of APTES pre-applied on the skin (see Figure 1).

Claims (9)

A method for cosmetic treatment of the skin, comprising:
_A compound or group of compounds _A that can condense in situ and exhibit at least one reactive functional group F _A that is free after condensation, and a covalent bond or physical (ionic) by reaction with the functional group F _A , look containing a reactive functional group F _C capable of forming a hydrogen) bonds, it is selected from phenyl benzimidazole sulfonic acid, terephthalylidene dicamphor sulfonic acid, phenyl dibenzimidazole tetrasulfonate disodium or mixtures thereof , Blocking agent C that blocks UV radiation
A method comprising applying to the skin.   The substance resulting from the condensation of A is soluble in water so that the blocking agent C reduces the solubility of the substance in water due to the reaction of the agent C with the substance resulting from the condensation of A. The method of claim 1, wherein   2. The method of claim 1, wherein the compound A comprises an organosilicon compound comprising 1-3 silicon atoms and at least two hydroxyl groups or hydrolyzable groups. The reactive functional groups F _A is a Amin A method according to claim 1 or 2. Compound A is represented by the formula:
(Where
R ₄ represents halogen or an OR ′ group or an R ′ ₁ group,
R ₅ represents halogen or an OR ′ group or an R ′ ₂ group,
R ₆ represents halogen or an OR ′ ″ group or an R ′ ₃ group,
R ₁ , R ₂ , R ₃ , R ′, R ″, R ′ ″, R ′ ₁ , R ′ ₂ and R ′ ₃ are independently of each other an additional chemical group such as an acid group or an amine group. Represents a straight-chain or branched and saturated or unsaturated hydrocarbon group, optionally with R ₁ , R ₂ , R ′, R ″ and R ′ ″ further representing hydrogen Is possible and
(At least two of the R ₄ , R ₅ and R ₆ groups are different from the R ′ ₁ , R ′ ₂ and R ′ ₃ groups)
The method according to any one of claims 1 to 3, corresponding to:   6. The method according to any one of claims 1 to 5, wherein A is γ-aminopropyltriethoxysilane (APTES) or one of its derivatives. In the first step, application of the compound or group A of the compound,
7. A method according to any one of claims 1 to 6 , comprising in a second step sequential application of the compound with application of the blocking agent C. The compounds A and C are mixed before application to the skin (mixing at the time of use) and the mixing is performed before application or during application to the skin (direct mixing on the area of the skin to be treated) 7. A method according to any one of claims 1 to 6 , wherein it is possible. at least,
A first composition comprising, in a physiologically acceptable medium, at least one compound or group A of compounds as defined in any one of claims 1 to 8 ;
Cosmetic assembly comprising a second composition comprising at least one blocking agent C as defined in any one of claims 1 to 8 in a physiologically acceptable medium.